EP2931784B1 - A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby - Google Patents
A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby Download PDFInfo
- Publication number
- EP2931784B1 EP2931784B1 EP13802566.3A EP13802566A EP2931784B1 EP 2931784 B1 EP2931784 B1 EP 2931784B1 EP 13802566 A EP13802566 A EP 13802566A EP 2931784 B1 EP2931784 B1 EP 2931784B1
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- EP
- European Patent Office
- Prior art keywords
- cyclic
- optionally
- monomer component
- polyester oligomer
- branched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 125000004122 cyclic group Chemical group 0.000 title claims description 159
- 238000000034 method Methods 0.000 title claims description 75
- 230000008569 process Effects 0.000 title claims description 70
- 229920000728 polyester Polymers 0.000 claims description 164
- 239000000203 mixture Substances 0.000 claims description 124
- 239000000178 monomer Substances 0.000 claims description 96
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 229920000642 polymer Polymers 0.000 claims description 39
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 34
- 239000003054 catalyst Substances 0.000 claims description 33
- 125000003118 aryl group Chemical group 0.000 claims description 32
- 150000007530 organic bases Chemical class 0.000 claims description 30
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 238000006384 oligomerization reaction Methods 0.000 claims description 28
- 229910052736 halogen Inorganic materials 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 150000002367 halogens Chemical class 0.000 claims description 26
- 230000035484 reaction time Effects 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 15
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 14
- 238000000926 separation method Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 125000004104 aryloxy group Chemical group 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 9
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 8
- 150000003973 alkyl amines Chemical class 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
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- 238000004821 distillation Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
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- 239000010936 titanium Substances 0.000 claims description 4
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- 239000011701 zinc Substances 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000005526 G1 to G0 transition Effects 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
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- 238000002425 crystallisation Methods 0.000 claims description 3
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- 239000001257 hydrogen Substances 0.000 claims description 3
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 241000894007 species Species 0.000 description 42
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 20
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- 229910001868 water Inorganic materials 0.000 description 13
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
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- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 description 7
- 239000005020 polyethylene terephthalate Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
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- 230000002378 acidificating effect Effects 0.000 description 6
- 230000002349 favourable effect Effects 0.000 description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 description 5
- 150000005690 diesters Chemical class 0.000 description 5
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 5
- 229920001707 polybutylene terephthalate Polymers 0.000 description 5
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000004035 construction material Substances 0.000 description 4
- PDSULNVJASBMLP-UHFFFAOYSA-N furan-2,5-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)O1 PDSULNVJASBMLP-UHFFFAOYSA-N 0.000 description 4
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 4
- 229920006158 high molecular weight polymer Polymers 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 0 *C(c1ccc(C(*COCCCCO)=O)[o]1)=O Chemical compound *C(c1ccc(C(*COCCCCO)=O)[o]1)=O 0.000 description 3
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229920013724 bio-based polymer Polymers 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000003818 flash chromatography Methods 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000903 polyhydroxyalkanoate Polymers 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229940086542 triethylamine Drugs 0.000 description 3
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NSQYDLCQAQCMGE-UHFFFAOYSA-N 2-butyl-4-hydroxy-5-methylfuran-3-one Chemical compound CCCCC1OC(C)=C(O)C1=O NSQYDLCQAQCMGE-UHFFFAOYSA-N 0.000 description 2
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000004255 ion exchange chromatography Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011968 lewis acid catalyst Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
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- 150000002972 pentoses Chemical class 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229920002961 polybutylene succinate Polymers 0.000 description 2
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
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- JABNNIJXMCCFAV-UHFFFAOYSA-N CC(c1ccc(C(C)=O)[o]1)O Chemical compound CC(c1ccc(C(C)=O)[o]1)O JABNNIJXMCCFAV-UHFFFAOYSA-N 0.000 description 1
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- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
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- 150000002632 lipids Chemical class 0.000 description 1
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- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- OIASAVWSBWJWBR-UKTHLTGXSA-N trans-2-[3-(4-tert-butylphenyl)-2-methyl-2-propenylidene]malononitrile Chemical compound N#CC(C#N)=CC(/C)=C/C1=CC=C(C(C)(C)C)C=C1 OIASAVWSBWJWBR-UKTHLTGXSA-N 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/91—Polymers modified by chemical after-treatment
- C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/916—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- Polyesters are an important class of commercial polymers with useful physical and mechanical properties and numerous applications. Polyesters find wide utility, for example, as fibres, coatings, films, or in composites. Most industrial polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyacrylates are produced from monomers derived from petrochemical feedstocks. Due to limited oil reserves, fluctuations of oil price, political instability in some production areas, and increased environmental awareness, there is growing interest for biobased polyesters produced from renewable feedstocks.
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- polyacrylates are produced from monomers derived from petrochemical feedstocks. Due to limited oil reserves, fluctuations of oil price, political instability in some production areas, and increased environmental awareness, there is growing interest for biobased polyesters produced from renewable feedstocks.
- the present invention achieves these objects and provides a solution to this problem by means of a process to prepare a cyclic oligomer composition
- a cyclic oligomer composition comprising a cyclic polyester oligomer having furanic units and having either structure Y 1 or Y 2 .
- These cyclic oligomers are prepared by condensation reactions carried out to high conversion and with linear impurities removed, and thus they do not contain carboxylic acid or free OH groups, as would monomers such as 2,5-furandicarboxlic acid or ethylene glycol, propanediol or butanediol. Therefore the further reaction of the cyclic oligomers of the invention to form a high molecular weight polymer will not release large amounts of water as do those monomers.
- a "catalyst” refers to an inorganic or metal-containing compound such as an organometallic species or a metal salt; whereas an “organic base” refers to a non-metallic and basic organic species.
- the claimed invention relates to a process to prepare a cyclic polyester oligomer composition
- a cyclic polyester oligomer composition comprising a cyclic polyester oligomer having furanic units, the cyclic polyester oligomer having either structure Y 1 or Y 2 : wherein A is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, and m is an integer from 1 to 20, preferably 2 to 15, most preferably 3 to 10, wherein each of the groups B is an optionally-substituted linear, branched or cyclic alkyl, phenyl, aryl, or alkylaryl, n' is an integer from 1 to 20, preferably 2 to 10, and m is an integer as defined above for Y 1 .
- the cyclic polyester oligomer composition of the current invention is not specifically limited and it may comprise other components in addition to the polyester polymer having furanic units and comprising the structure Y 1 or Y 2 .
- the cyclic polyester oligomer composition may additionally comprise small amounts of one or more unreacted and/or unremoved reaction components such as a monomer component (unreacted diacid, diol, or acidol reagents), a catalyst, a templating agent, a base, a catalyst quencher, a solvent, used in the preparation of the cyclic polyester oligomer.
- the catalyst and/or organic base is present, and the catalyst is present in an amount relative to the total weight of the monomer components of from 1 ppm to 1 weight%, preferably from 10 to 1,000 ppm, more preferably from 50 to 500 ppm, and the organic base is present in a stoichiometric ratio of from 0.5 to 6, preferably 1 to 4, more preferably 2 to 3 mol relative to 1 mol of all monomer component species used as a reactant in the process.
- concentration of the catalyst and the organic base may be readily determined by the masses or mass flow rates used of these reagents relative to that of the monomer components.
- the apparatus suitable for carrying out the oligomerization process of the invention is not specifically limited.
- batch reactors, stirred tank reactors, plug flow reactors, static mixers, cascades of stirred tank reactors, and continuous flow stirred tank reactors may all be used.
- linear oligomeric polyester species having furanic units are generally present in an amount of less than 5 wt. %, more in particular in an amount of less than 3 wt.%, still more in particular in an amount of less than 1 wt.% relative to the total weight of the cyclic polyester oligomer composition.
- the content of linear oligomeric polyester species having furanic units in the cyclic polyester oligomer composition of the invention may be readily determined by conventional methods.
- the content of linear oligomeric species may be determined by electrospray mass spectrometry, matrix-assisted laser desorption/ ionization (MALDI) mass spectrometry, high-performance liquid chromatography (HPLC) method coupled to mass spectronomy, and gel filtration chromatography.
- concentration of linear oligomeric polyester species having furanic units refers to the concentration as determined by HPLC.
- the reactor was heated to 190°C and temperature was raised gradually to 220°C under nitrogen, while excess diol distilled off. After 1.5 hour 2.5 mL of fresh diol was added and the reaction was continued again for 1.5 hours, distilling off the excess diol. The reaction was indeed cooled to 190°C, vacuum was applied and the reactor was sealed. The reaction was continued for 2 hours at this temperature. Finally, 1 mg of of Ti(OBu) 4 was added and the reaction continued for 3 h at 220°C in vacuum. Reaction was quenched by concentration to dryness. Polyester oligomers were washed with chloroform, to remove catalyst traces. Next they were suspended in hexane, recovered by vacuum filtration and used without additional purification in the following ring-closing reaction.
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EP13802566.3A EP2931784B1 (en) | 2013-03-15 | 2013-11-27 | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby |
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PCT/EP2013/074883 WO2014139603A1 (en) | 2013-03-15 | 2013-11-27 | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby |
EP13802566.3A EP2931784B1 (en) | 2013-03-15 | 2013-11-27 | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby |
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US (1) | US9725558B2 (zh) |
EP (1) | EP2931784B1 (zh) |
JP (2) | JP6427507B2 (zh) |
KR (1) | KR102101280B1 (zh) |
CN (1) | CN105189603B (zh) |
BR (1) | BR112015020539B8 (zh) |
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JP6416134B2 (ja) * | 2013-03-15 | 2018-10-31 | スルザー ケムテック アクチェンゲゼルシャフト | フラン単位を有するポリエステルポリマーを含むポリエステルポリマー組成物を調製する方法、並びにそれにより得られるポリエステルポリマー組成物及びその使用 |
CN107840946B (zh) * | 2016-09-19 | 2020-02-07 | 中国科学院宁波材料技术与工程研究所 | 一种生物基高分子化合物及其制备方法 |
CN107840948B (zh) * | 2016-09-19 | 2020-02-07 | 中国科学院宁波材料技术与工程研究所 | 一种生物基高分子化合物及其制备方法 |
EP3301091A1 (en) | 2016-09-29 | 2018-04-04 | Sulzer Chemtech AG | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it |
EP3392288A1 (en) | 2017-04-21 | 2018-10-24 | Sulzer Chemtech AG | A process to prepare a cyclic oligomer and a cyclic oligomer obtainable thereby and a process to polymerize it |
WO2018060241A1 (en) | 2016-09-29 | 2018-04-05 | Sulzer Chemtech Ag | A process to prepare a polyester polymer and a polyester polymer obtainable thereby |
EP3564437A4 (en) * | 2016-12-28 | 2019-12-25 | Asahi Kasei Kabushiki Kaisha | WATER ABSORBING POLYESTER FIBER COATED YARN BODY AND MANUFACTURING METHOD THEREOF |
JP7067959B2 (ja) * | 2017-03-08 | 2022-05-16 | 三洋化成工業株式会社 | 環状化合物組成物及びその製造方法 |
US10353853B1 (en) * | 2018-04-11 | 2019-07-16 | Cypress Semiconductor Corporation | USB type-C sideband signal interface circuit |
CN116693497B (zh) * | 2023-08-01 | 2023-10-10 | 苏州大学 | 一种芳香族聚酯的解聚成环方法 |
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GB621971A (en) | 1946-11-12 | 1949-04-25 | James Gordon Napier Drewitt | Improvements in polymers |
US5039783A (en) * | 1990-11-05 | 1991-08-13 | General Electric Company | Method for preparing and polymerizing macrocyclic poly(alkylene discarboxylate) oligomers |
US5446122A (en) * | 1994-11-30 | 1995-08-29 | General Electric Company | Process for preparing macrocyclic polyesters |
US6420047B2 (en) * | 2000-01-21 | 2002-07-16 | Cyclics Corporation | Macrocyclic polyester oligomers and processes for polymerizing the same |
US20070216067A1 (en) * | 2000-01-21 | 2007-09-20 | Cyclics Corporation | Macrocyclic polyester oligomers as carriers and/or flow modifier additives for thermoplastics |
JP2004507599A (ja) * | 2000-09-01 | 2004-03-11 | サイクリクス コーポレイション | 線形ポリエステルを、大環状オリゴエステル組成物および大環状オリゴエステルに変換する方法 |
DE102004023900A1 (de) | 2004-05-12 | 2005-12-01 | Woco Industrietechnik Gmbh | Verfahren zur Herstellung von polymeren Verbundmaterialien sowie die nach diesem Verfahren enthaltenen Verbundmaterialien |
JP4881127B2 (ja) * | 2005-11-07 | 2012-02-22 | キヤノン株式会社 | 高分子化合物およびその合成方法 |
JP5371259B2 (ja) * | 2008-02-20 | 2013-12-18 | キヤノン株式会社 | ポリエステル樹脂、その製造方法、成形品用組成物及び成形品 |
JP2009215467A (ja) * | 2008-03-11 | 2009-09-24 | Canon Inc | ポリエチレン−2,5−フランジカルボキシレートの製造方法 |
NL2002382C2 (en) * | 2008-12-30 | 2010-07-01 | Furanix Technologies Bv | A process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers. |
CN102050941B (zh) * | 2009-11-03 | 2013-12-11 | 东丽纤维研究所(中国)有限公司 | 一种高分子聚合物及其生产方法 |
BR112014016453A8 (pt) * | 2012-01-04 | 2017-07-04 | Pepsico Inc | poliésteres à base de ácido 2,5-furan dicarboxílico preparados a partir da biomassa |
JP5939638B2 (ja) * | 2012-12-12 | 2016-06-22 | 花王株式会社 | ポリエステル系トナー用結着樹脂組成物 |
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CN105189603A (zh) | 2015-12-23 |
RU2648995C2 (ru) | 2018-03-29 |
JP6505917B2 (ja) | 2019-04-24 |
BR112015020539B8 (pt) | 2022-10-18 |
KR20150130999A (ko) | 2015-11-24 |
JP6505917B6 (ja) | 2019-05-29 |
US9725558B2 (en) | 2017-08-08 |
JP2016512811A (ja) | 2016-05-09 |
CN105189603B (zh) | 2017-10-17 |
EP2931784A1 (en) | 2015-10-21 |
JP6427507B2 (ja) | 2018-11-21 |
TW201500399A (zh) | 2015-01-01 |
WO2014139603A1 (en) | 2014-09-18 |
JP2018141013A (ja) | 2018-09-13 |
KR102101280B1 (ko) | 2020-05-27 |
BR112015020539B1 (pt) | 2021-05-18 |
RU2015137713A (ru) | 2017-04-20 |
US20160017093A1 (en) | 2016-01-21 |
BR112015020539A2 (pt) | 2017-07-18 |
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